Note: Descriptions are shown in the official language in which they were submitted.
-- 1 --
6-152~1/8/CGC 1120
Perfluoroalkyl-alkylthio-, -sulfinyl- or -sulfonyl-alkylene
glycidyl ethers, a process for their production and their use
The instant inventlon i8 directed to novel perfluoroalkyl-alkyl-
thio-, -sulfinyl- or -sulfonyl-alkylene glycidyl ethers of the
formula I
Rf-R1-S(O)m-R-OCH2C ~ /CH2 (I),
wherein
Rf is straight or branched chain perfluoroalkyl of 3 to 18 carbon
atoms or perfluoroalkoxyperfluoroalkyl of 3 to 18 carbon atoms;
R1 is straight or branched chain alkylene of up to six carbon atoms,
carboxamidalkylene of up to six carbon atoms, or sulfonamldoalkylene
of up to six carbon atoms, and wherein the amido nitrogen thereof is
unsubstituted or substituted by lower alkyl;
m is 0, 1 or 2; and
R is straight or branched chain alkylene of 2 to 12 carbon atoms.
Lower alkyl means alkyl groups, having 1 to 6, preferably 1 to 4
carbon atoms.
Preferably Rf is perfluoroalkyl. More preferably Rf i9 straight
chain perfluoroalkyl. Especially the Rf radical contains 6 to 12
carbon atoms. Mixtures of perfluoroalkyl groups are often advan-
tageous.
24L~S7
Rl is preferably straight chain alkylene of 2 to 6, especially 2 to
4 carbon atoms and most preferably ethylene.
The group m is preferably O or 2.
R is preferably straight or branched chain alkylene of 2 to 6,
especially 2 to 4 carbon atoms. Most preferably R is straight or
branched chain alkylene of 3 carbon atoms.
The compounds of formula I may be prepared by methods generally
known to the art.
For example, the compounds of formula I where m is O may be prepared
by reactlng a mercaptan of the formula II
Rf-R1-SH (II),
where Rf and R1 are as defined above, wlth alkenyl glycidyl ethers
of the formula III
R'-OCH2CH 7 CH2 (III),
o
where R' is alkenyl of 2 to 12 carbon atom~ corresponding to the
alkylene group R in formula (I). This reaction ls conveniently
carried out ln the presence of a free-radical catalyst, such as an
azo type free-radlcal catalyst.
The reactlon temperature and choice of azo-type free-radical
catalyst are considered to be mutually dependent. The temper2ture
range of 40C to 100C is one wherein the formation of undesirable
by-products is minimized and wherein the reactlon products are
stable. In order to achieve a reasonable reaction rate of these
temperatures, lt is deslrable to use an azo-type catalyst that is
reactive to a reasonable extent in thls temperature range. It is,
therefore, preferred to use an azo-type free-radical catalyst havlng
a 1-hour half-life temperature of 40 to as high as 100C.
~2~57
Suitable inert solvents are auch in which the reactants are soluble
at reaction temperatures and include aliphatic or aromatic hydro-
carbons such as heptane, methylcyclohexane, benzene, toluene;
chlorinated or fluorinated aliphatic or aromatic hydrocarbons such
a~ methylene chloride, chloroform, methyl chloroform, carbon
tetrachloride, trlchloroethylene, perchloroethylene, Freons such as
1,l,2-trifluoro-l,2,2-trichloroethane, chlorobenzene, benzotri-
fluoride or tetrafluoroxylene; ketones, esters and ethers such as
acetone, methyl isobutyl ketone, ethyl acetate and higher homologs,
dialkyl ethers, tetrahydrofuran, ethylene glycol moDomethyl or
monoethyl ether, ethylene glycol dimethyl or diethyl ether; and
nitriles such as acetonitrile.
Where convenient, it is preferred to carry out the addition reaction
in bulk, i.e. in the absence of a solvent.
Whlle the choice of conventional azo-type free-radical catalyst is
not critical, 2,2'~azobis (2,4-dimethylvaleronitrile) has been found
convenient.
An alternate method of preparing the compounds of formula I involves
the sddition of an alcohol of the formula IV
Rf-Rl-S(O)m-R-OH (IV),
where Rf, Rl, m and R are as defined above, with an epihalohydrin of
the formula V
X-CH2-C ~7 CHz (V),
o
where X is halo, preferably chloro, to form the corresponding
halohydrin VI
Rf-Rl-S(0) -R-OCHz8H-CH2X (VI),
~Z4~4~i7
where Rf, Rl, m, R and X are defined above, followed by dehydro-
halogenatlon to remove the hydrogen halide, HX, and form the
corresponding glycidyl ether of formula I.
In this alternate method of preparing the compounds of formula I,
the alcohol of formula IV is reacted with the halohydrin, such as
epichlorohydrin, in bulk or in a common dry and aprotic solvent,
including ketones, such as acetone or methyl ethyl ketone; ethers,
such as dlethylether, ethyleneglycol-dimethylether or tetrahydro-
furan; esters such as ethyl acetate or methyl cellosolve acetate;
aromatic hydrocarbons, such as benzene or toluene; and amides or
lactames, such as dimethylformamide or N-methyl pyrrolidone. A Lewis
acid catalyst, such as boron trifluoride (usually in the form of the
diethyl ether complex thereof) or allminum chloride, is used to
promote the formation of the halohydrin intermediate. If the
reaction i8 run in the absence of a solvent, it is advantageously
run at a temperature above the melting point of the compound with
boron trifluoride-etherate. The reaction is ordinarily exothermic.
It is generally not necessary to isolate the halohydrin interme-
diate, and the dehydrohalogenation can be carried out in the same
reaction vessel to form the gylcidyl ether of formula I.
The dehydrohalogenation of the halohydrin of formula VI to form the
glycidyl ether of formula I is advantageously achieved by contacting
the halohydrin of formula VI with a base, preferably using a
stoichiometric amount, or slight excess of base.
Suitable bases include sodlum hydroxide, potassium hydroxide,
pyridine, lutidine and triethylamine. Convenlently, a solvent is
selected which dissolves the reactants and desired product, but not
the by-product salt 9 SO that the salt will precipitate out as the
reaction proceeds and can then be removed by conventional tech-
niques, such as filtration.
1457
-- s --
The dehydrohalogenation reactlon i8 conveniently conducted between
about 20C and 100C in aqueous/organic media, such as an
aqueousllower alkanol media or aqueous/organic hydrocarbon media
such as aqueous/toluene medla. When the reactlon i8 conducted ln a
two phase medlum a phase transfer catalyst such as a di-dodecyl
dlmethyl ammonlum hydroxide or tetrabutylammonium hydrogen sulfate
can be employed to accelarate the reaction.
Typically, a stoichiometric amount of a base, ~uch as 50% aqueous
sodium hydroxlde, is slowly added to the reaction mixture. The
resulting reaction is exothermic and the reaction temperature is
advantageously maintained between about 20-60C with stirring for
a time, for example 1-3 hours, sufficient to form the desired
epoxide of the formula (I).
The by-product salt i3 removed from the epoxide intermediate and any
residual solvent is removed by vacuum distillation. The product may
be used without further puriflcatlon or distilled lf necessary.
The instant perfluoroalkyl group containing epoxides are very
reactive and can be used to prepare highly surface-active fluoro-
surfactants.
Thus, the compounds of formula I can be reacted with amine sulfur
trloxide complexes, such as trimethylamine sulfur trioxide,
N-methylpyrrolidone-sulfur trioxide, and the like, to form useful
surfactants having low surface and interfacial tension prQperties.
The reaction can be performed in accordance with the general and
specific disclosures set forth in U.S. Patent 4,435,330. The
resulting sulfato betaine surfactants find utility as cleaning
agents, as leveling agents for floor waxes and as aqueous wetting
agents in fire-fighting compositions.
Suitable amine sulfur trioxide complexe~ for use in reaction with
tne compounds of formula I are complexes of the formula VII
S~
- 6 -
R6 ~ I-SO3 (VII),
wherein Rs, R6 and R7 are independently lower alkyl, and R6 may also
represent benzyl, and R6 and R7 taken together with the nitrogen to
which they are attached may also represent piperidino or morpholino,
or Rs, R6 and R7 taken together with the nitrogen to which they are
attached, may represent pyridyl, acridyl or quinolyl. The reactlon
between the glycidyl ethers of formula I and the amine sulfur
trioxide complexes of formula VII advantageously takes place by
reacting stoichlometric amounts of each at a temperature between 30
and 180C, optionally in the presence of a solvent, such as
N-methylpyrrolidone.
Alternately, the compounds of formula I can be reacted with an amino
acid of the formula VIII
Ra\
~ -Z (VIII)
Rg
wherein Rg and Rg are hydrogen, or lower alkyl; and Z is alkylene of
up to 12 carbon atms which is substituted by carboxy, sulfo,
phosphoro or phosphono. Suitable compounds of formula VIII include
glycine, alanine, aspartic acid, sarcosine, 2-aminoethyl hydrogen
pho3phate, taurine and methyl taurine. Sulfo, phosphoro or phosphono
means acidic groups, containing sulfur or phosphor, which are linked
through an oxygen atom or directly via the sulfur or phosphor atoms
to the alkylene of the group Z. Examples are -S(O)OH, -S(O)zOH,
-OS(O)OH, -OS(02)0H, -P(OH)2, -P(O)(OH)2, -OP(OH)2, -OP(O)(OH)z.
The addition of glycidyl epoxide of formula I to amino acid of
formula VIII is a base catalyzed 1:1 reaction which occurs most
readily in a single phase. This is generally provided in an aqueous
solvent mixture by choice of a suitable water miscible cosolvent
~.;29Lf~5~
such as methanol, isopropanol, butoxyethanol and the like. The
reaction ls generally conducted at temperatures from 25 to 200C,
but preferably from 50 to 130C.
The reactlon can be run uncatalyzed if the reactant is sufflclently
baslc or at an alkallne pH provlded by alkall hydroxlde, lon ex-
change catalyst or a non-reactlve base, e.g. trllsopropylamine.
The products are generally useful without isolation but can be
isolated depending on the pH, in acid form, as isoelectronic neutral
salts or as alkali metal or ammonium salt3. The fully quaternized
derivatlves containing N lower alkyl or N-benzyl quaternary func-
tiona are generally isolated as neutral 2witterionic compounds or
acid adducts, e.g. hydrochlorides.
The resulting amphoteric compounds are very stable to hydrolysis and
find numerous uses as surfactancs and wetting agent~. Slnce they are
derlved from readlly available amlno acids and certain readily
available fluorinated epoxides they comprlse partlcularly useful
compositions.
The alcohols of formula IV are known or can easily be prepared from
known compounds by methods known per se. Thus, for example, the
alcohols of formula IV can easily be prepared by reacting a mer-
captan of formula (II), as de~cribed above, with either a halo-
alkanol of the formula IX
X-R-OH (IX),
where X and R are as defined above, or an unsaturated alcohol OL the
formula X
R'-OH (X),
wherein R' is defined above.
~'~4a~4S7
-- 8 --
The reaction between II and IX can easily be performed by reacting
stochiometric amounts of each in the presence of a base to remove
the acid halide (HX) formed, in the presence or absence of an inert
solvent, at a reation temperature between 30C and 120C? and
removing the by-product salt, e.g. by washing with water. Suitable
bases include alksli metal hydroxides and carbonates, alkaline earth
metal hydroxides and carbamates and amines such as trimethylamine or
pyrldine. Sufficient base should be added during the course of the
reaction to react with all hydrogen halide formed. Where employed,
suitable inert solvents include tetrahydrofuran, dimethylsulfoxide,
lower alkanols and the like.
In reacting the mercaptsn o~ formula II with an unsaturated alcohol
of formula X to obtain the corresponding alcohol of formula IV, the
simple addition reactlon is conveniently conducted in the presence
of 8 free radical initiator, such as an azo-type free-radical
initiator, for example 2,2'-azobis (2,4-dimethylvaleronitrile), in
the presence or absence of an inert solvent such as tetrahydrofuran,
methyl ethyl ketone, dimethylsulfoxide or the like, at a reaction
temperature between about 30 and 100C.
In order to obtain those compounds of formula IV wherein m equals l
or 2 from the corresponding thioether alcohol, where m equals 0, the
thioether alcohol of formula IV is oxidized with an oxidizing agent.
Suitable oxidizing agents includ0 hydrogen peroxide in an organic
scid medium, such as acetic acid. The reaction is conducted at a
temperatu~e of between about 30C to 100C until the thioether
alcohol i8 converted to the corresponding sulfoxide or sulfone. In
general, lower temperatures e.g. between about 30C and 50C favor
the formation of the sulfoxide, where m ~ 1, whereas more elevated
temperatures, e.g. between about 50C and 100C, favor the forma-
tion of the corresponding sulfones. Moreover, the formation of
~2~L457
sulfoxide can be enhanced by reducing the amount of peroxide
employed to a 1:1 mole ratio, whereas a substantial excess of
peroxide generally favors the formation of sulfones.
Simllarly, the compounds of formula I wherein m equals 0 can be
converted into the corresponding sulfoxides and sulfones, i.e. where
m is 1 or 2, by oxidation with a suitable oxidizing system which
does not affect the glycidyl moiety, such as a perbenzoic acid, a.g.
meta-chlorperbenzoic acid, in the presence of an inert solvent, such
as a halogenated hydrocarbon, e.g. chloroform, or the like, at a
reaction temperature between about 10C to about 50C. Again
elevated temperatures and an excess of peroxide ~avor the formation
of sulfone.
The present invention is more clearly understood with reference to
the following non-limiting Examples. All parts are by weight unless
otherwise speclfied.
Example 1: A mixture of 1-allyloxy-2,3-epoxy propane (24.1 g,
0.212 mol) and 2,2'-azobis (2,4-dimethylvaleronitrile) (0.99 g,
0.004 mol) is added dropwise between 60-75C within 40 minutes
under nitrogen to a solutlon of 1,1,2,2-tetrahydroperfluoro-
octane)thiol (77.26 g, 0.202 mol) in 11 g toluene. The reaction
mixture is stirred for 3 hours at 65-70C and the toluene distil-
led off at 80C under aspirator vacuum (25 mm) to yield ~9.2 g (99 %
of theory) of a clear colorless liquid in a 10:1 ratio of the
isomers I and II.*
*I C6Fl3cHzcHzscH2cH2cHzocH2cH\ /CHz
II C6F13CHzCH2SlCH2CH20CH2\ /CHz
H3 0
~ ;~2~57
-- 10 --
Titration with perchloric acid in the presence of tetrabutylammonium
iodide results in an equivalent mol weight of 509 (theory 494). NMR
shows proton resonances at ~ 1.85, 2 protons (-SCH2CH2CH20); C
2.37, 2 protons ~C6F13CH2CH2)- 6 2.69, 6 protons (C6F13CH2CH2SCHz
CH\-/CH2); ~ 3.11, 1 proton (C_\-/CH2);
~ 3.33 and 6 3.71,2 protons (0-CH2); and ~ 3.57 (CH20CH2).
Analysis for C14H1sF13O2S:
Calc: C, 34.0; H, 3.0
Found: C, 33.9; H, 3.0
Example 2: 1,1,2,2-tetrahydroperfluoroalkylthiol (distribution
represents a mixture of 2.1 % C4, 37.6 % C6, 34.3 % Cg, 19.0 % C
5.5 % C12, 1.0 % C14) (279.6 g; 0.615 mol) and a solution of
1-allyloxy-2,3-epoxypropane (73.6 g; 0.646 mol) and 2,2'-azobis (2,4
dimethylvaleronitrile) 3.0S g; 0.012 mopl) are added parallel under
nitrogen at 60C within 90 minutes through two separate additlon
funnels into a reaction flask. ~he reaction mixture is stirred for
another hour at 60C to yield 342.7 g (98 % of theory) as a slight
yellow gel. GC Analysis showed 99 % assay in a 10:1 ratio of the
isomer I and II.*
*I RfCH2CH2SCH2CH2CH20CH2C~ /CH2
o
CH3 0
Titration with perchloric acid in the presence of tetrabutylammo-
niumiodide results in an equivalent mol weight of 573 (theory 569).
NMR shows the same proton resonances as in example 1.
Example 3: 1,1,2,2-tetrahydroperfluoroalkylthiol (distribution
represents a mixture of 0.2 % C4, 0.4 % C6, 8.4 % Cs, 28-0 % C1o,
39.1 % C12, 18.1 % C14, 4.3 % C16) (90.0 g. 0.138 mol) is metered
parallel with a solution of 2,2'-azobis-(2,4-dimethylvaleronitrile)
(0.8 g, 0.003 mol) and 1-allyloxy-2,3-epoxy propane (16.5 g,
~Z~57
0.145 mol) in two separate feeds between 65-70C under nitrogen
into a reaction flask, charged with 24 g toluene. The reactlon is
stlrred at 85C for 90 minutes and the toluene evaporated at room
temperature under high-vacuum to yield 100.4 g (95 % of theory) as a
white crystalllne ~olid with a melting point of 78-107. GC
Analysis shows a 99 % assay in a 10:1 ratio of the isomers I and
II.*
*I RfCH 2 CH 2 SCR 2 CH 2 CH2OCH2CH\ /CHz
II RfCH2CH2S,CHCH2OCH2C ~7 CH2
Titration with perchloric acid in the presence of tetrabutylammo-
niumiodide results in an equivalent mol weight of 756 (theory 767).
Example 4: A solution of m-chloroperbenzolc acid ~64.8 g 80 %,
0.3 mol) in 800 ml chloroform is added dropwlse under nitrogen
wlthin 5 hours to an isomeric mixture of 1-[(1,1~2,2-tetrahydro-
perfluoro-octylthio)-l-propyloxy]-2,3-epoxy propane and
1-[(1,1,2,2-tetrahydroperfluoro-octylthio]-2-propyloxy]-2,3-epoxy
propane (74.1 g, 0.15 mol) dissolved in 400 ml chloroform. The
slight exothermic reaction is kept between 25-35C durlng the
addition and stirred at room temperature overnight. The precipitated
m-chlorobenzoic acid is filtered off and the filtrate washed twice
with ice cold 10 % NaOH, once with ice cold brlne and once with
ice-water. The organic layer is dried over MgSO4, evaporated to
dryness and dried under high vacuum overnlght to yield 73.5 g (93 %
of theory) as a whlte crystalline solid with a melting point of
61-64 (103 clear). GC Analysis shows a 94 % assay in a 10:1
ratio of the isomer I and II.*
*I C6F13CH2CHzSO2CH2CH2CH2OCH2CH\ /CHz
II C6F13CH2CH2SO2,CHCH2OCH2CH\ /CH2
H3 O
~2~57
- 12 -
Titration with perchloric acld in the pre~ence of tetrabutylammo-
niumiodide result~3 in an equivalent mol weight of 534 (theory 526).
NMR shows proton resonances at ~ 2.13, 2 protons (S02CH2C_2CH20-);
2.57, 1 proton (CH\-/CHz);
2.76, 2 protons (C6F13CH2); ~ 2.77, I proton (C ~-/C_2);
3.11, 1 proton (C~ -/CH2); ~ 3.23 4 protons (C6F13CH2CH2S02CH2);
3.31, 1 pro~on (O-C_2CH); ~ 3.63 2 protons (SO2CH2CH2C_2) and
~ 3.79, 1 proton (O-C_2CH).
Analysis for C14H1sF1304S
Calc: C, 31.9; H, 2.85
Found: C, 33.1; H, 2.9
Example 5: A 10:1 isomeric mixture of 1-1(1,1,2,2-tetrahydroper-
fluorooctylthio)-1-propyloxy]-2,3-epoxy propane and 1-[(1,1,2,2-
tetrahydroperfluorooctylthio-)-2-propyloxy]-2,3-epoxy propane
(14.8 g, 0.03 mol) in 42.2 g 2-propanol and 10 g deionized water is
reacted at 60C for 5 hours with N-methyltaurine-sodium salt (11.4 g
42.2 % in H20; 0.03 mol) under nitrogen. The clear yellow solution
is dialized for 24 hours and the water removed in a draft-oven at
80C, the yellow residual gum dissolved in hot acetone, evaporated
and dried under high vacuum overnight to yield an amorphous residue.
Analysis for C~7Hz3Fl3NOPsS2Na
Calc: C, 31.8; H, 3.58; N, 2.18; F, 38.5
Found: C, 31.6; H, 3.5; N, 2.0; F, 38.5
Isomeric mixture of
C6Fl3CH2CH2SCH2CH2CH20CH2fHCH2~CH2CH2SO3Na
C6F13CH2CH2S~HCH20CH21CHCH2~CH2CH2SO3Na
CH3 OH CH3
457
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